JP3755732B2 - Method for producing porous group 4 metal oxide - Google Patents
Method for producing porous group 4 metal oxide Download PDFInfo
- Publication number
- JP3755732B2 JP3755732B2 JP2000213535A JP2000213535A JP3755732B2 JP 3755732 B2 JP3755732 B2 JP 3755732B2 JP 2000213535 A JP2000213535 A JP 2000213535A JP 2000213535 A JP2000213535 A JP 2000213535A JP 3755732 B2 JP3755732 B2 JP 3755732B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- group
- catalyst
- oxide
- metal oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 43
- 150000004706 metal oxides Chemical class 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 55
- 239000002184 metal Substances 0.000 claims description 55
- 239000002245 particle Substances 0.000 claims description 43
- 239000003966 growth inhibitor Substances 0.000 claims description 41
- 150000001768 cations Chemical class 0.000 claims description 19
- 239000000017 hydrogel Substances 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- -1 Oxy anion Chemical class 0.000 claims description 15
- 238000010304 firing Methods 0.000 claims description 13
- 150000001450 anions Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 5
- 150000004692 metal hydroxides Chemical class 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 141
- 239000003054 catalyst Substances 0.000 description 103
- 239000011148 porous material Substances 0.000 description 39
- 230000000704 physical effect Effects 0.000 description 32
- 238000000034 method Methods 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 28
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000011733 molybdenum Substances 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910000348 titanium sulfate Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910000347 yttrium sulfate Inorganic materials 0.000 description 2
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- QGBLCIBATKETJC-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;manganese(2+) Chemical compound [Mn+2].O1B([O-])OB2OB([O-])OB1O2 QGBLCIBATKETJC-UHFFFAOYSA-N 0.000 description 1
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- FLVFLHZPYDNHJE-UHFFFAOYSA-N chloro hypochlorite;hafnium Chemical compound [Hf].ClOCl FLVFLHZPYDNHJE-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- NXKAMHRHVYEHER-UHFFFAOYSA-J hafnium(4+);disulfate Chemical compound [Hf+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NXKAMHRHVYEHER-UHFFFAOYSA-J 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- AKEKKCGPLHMFCI-UHFFFAOYSA-L potassium sodium hydrogen carbonate Chemical compound [Na+].[K+].OC([O-])=O.OC([O-])=O AKEKKCGPLHMFCI-UHFFFAOYSA-L 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 description 1
- UXBZSSBXGPYSIL-UHFFFAOYSA-K yttrium(iii) phosphate Chemical compound [Y+3].[O-]P([O-])([O-])=O UXBZSSBXGPYSIL-UHFFFAOYSA-K 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、触媒担体、触媒、乾燥剤、吸着剤、充填剤等の用途に有用な多孔質４族金属酸化物とそれらを製造するための方法及びその用途に係るもので、特に、高比表面積でかつ熱安定性にも優れた多孔質４族金属酸化物水素化処理用触媒担体と触媒、及びそれらの製造方法並びにその用途に関する。
【０００２】
【従来の技術】
従来、多孔質４族金属酸化物は、例えば、液相における水酸化チタンの一般的な合成方法である硫酸チタン(硫酸チタニル)溶液を加水分解する方法、四塩化チタンあるいは硫酸チタン(硫酸チタニル)等の水溶液をアルカリで中和する方法、チタンアルコキシドを加水分解するゾル・ゲル化方法等で生成させた４族金属含水酸化物を乾燥・焼成して製造されている。
【０００３】
しかしながら、このような従来法で製造されるチタニアについては、熱安定性が悪く、図１の比表面積と焼成温度の関係に示す如く、焼成温度が高くなるにつれて、その比表面積が急激に低下し、高比表面積を維持することが困難であった。これは、この高温焼成の過程で、いわゆるシンタリングや脱水縮合により粒子の成長が起こるためである。例えば、含水酸化チタンの場合は、シンタリングや脱水縮合により無定形からアナタース、ルチル等への結晶化や結晶転移が起こり、図１のように比表面積が激減してしまう。
【０００４】
このため、例えば、従来技術によって製造されるチタニア担体あるいはチタニア触媒は、炭化水素の水素化処理用触媒として単位比表面積当たりの水素化処理活性が非常に優れているにも拘わらず、アルミナやシリカ系の触媒担体或いは触媒のようには工業的に利用されることがなかった。また、例えば、アルキレーション用触媒として用いる場合には、超強酸としての酸性質を発現させるために高温処理する必要があるが、従来の担体では熱安定性が悪く低比表面積になるため、その酸の絶対量が少なくなり触媒としての必要性能を確保することができなかった。また、排煙脱硝用触媒として用いる場合にも、単位比表面積当たりの脱硝活性が非常に優れているにも拘わらず、熱安定性の問題から通常４０〜５０ｍ2／ｇの低比表面積でしか使用できないため、多量の触媒を必要としているのが現状である。更に、この熱安定性の問題のため適用の温度範囲が狭いという問題もあった。また、チタニアについては、その摩耗強度が高いにもかかわらず、フィシャー・トロプシュ（ＦＴ）反応用触媒として用いる場合は、低比表面積のものしか得られないため性能的に満足の行く触媒が得られていないのが現状である。そのため、従来技術によって製造されるチタニア担体及び触媒は、その使用目的や使用条件等によって要求される性能を十分満足させることができない。すなわち、熱安定性が悪いために高温において高比表面積が維持できず性能が悪いものとなっているという問題があった。
【０００５】
また、上述した従来法ではシャープな細孔径分布を有するチタニアを製造することは困難であった。一般的に、高性能を有する触媒の細孔径の範囲は、対象とする反応物質に適した細孔径に制御することが必要である。すなわち反応物質の拡散抵抗がなく、かつ反応に有効でない小さなあるいは大きすぎる無駄な細孔を持たないことが重要である。このため、反応の目的に合わせて細孔径が制御された触媒であることが理想的である。例えば、反応に有効な触媒細孔径は、軽油の脱硫を目的とした場合には６〜１０ｎｍであり、重質油の脱硫を目的とした場合には８〜１５ｎｍであり、脱メタルを目的とした場合には１５〜３０ｎｍであり、脱アスファルテンを目的とした場合には２０〜４０ｎｍの範囲にある。しかし、従来法によって製造されるチタニア触媒については、反応に最適な触媒細孔径が少ないために、反応の選択性や活性及び触媒寿命の点で十分な性能が得られないという問題等もあった。
【０００６】
そこで、このような問題を解決し、細孔径分布をシャープにし細孔径の範囲を制御するための方法として、例えば特公昭６０−５０,７２１号公報において、種子となるヒドロゾルを得る工程と、このヒドロゾルのｐＨを、ヒドロゾル溶解領域とヒドロゾル沈殿領域との間で交互に変動させ、これによって結晶を成長させて疎凝集体を形成したヒドロゾルを得る工程と、この疎凝集体を形成したヒドロゾルを乾燥し、焼成して金属酸化物を得る工程とを有する多孔質無機酸化物の製造方法が提案されている。
【０００７】
しかしながら、単にこの方法のみでは、例えば、チタニアについて制御されたシャープな細孔径分布を有することはできるが、触媒の焼成や反応系での反応熱等による熱履歴に対しても活性低下を起こさないようなチタニア触媒を製造することは困難であった。
【０００８】
【発明が解決しようとする課題】
そこで、本発明者らは、熱安定性にも優れ比表面積が大きい、多孔質４族金属酸化物とそれを製造する方法について鋭意検討した結果、一般式ＭＯ2・ｎＨ2Ｏ（但し、Ｍは４族金属を示し、ｎは０．０２以上である）で表される４族金属含水酸化物のヒドロゾル又はヒドロゲル若しくはそれらの乾燥物に、粒子成長抑制剤として１種又は２種以上のアニオン、又はカチオン、若しくはこれらアニオン及びカチオンを添加したのち、乾燥、焼成することにより、熱安定性に優れ、８０ｍ2／ｇ以上の高い比表面積を有し、かつ触媒金属が高分散している多孔質４族金属酸化物が得られることを見出し、本発明を完成した。
【０００９】
従って、本発明の目的は、熱安定性に優れ比表面積が大きく、触媒金属が高分散されている多孔質４族金属酸化物とその製造方法及びその用途を提供することにある。
【００１０】
また、本発明の他の目的は、熱安定性に優れ比表面積が大きく、かつ触媒金属の高分散に加え、制御されたシャープな細孔径分布を持ち優れた反応選択性を有する触媒又は触媒担体として有用な多孔質４族金属酸化物とその製造方法及びその用途を提供することにある。
【００１１】
【課題を解決するための手段】
すなわち、本発明は、一般式ＭＯ2・ｎＨ2Ｏ（但し、Ｍは４族金属を示し、ｎは０．０２以上である）で表される４族金属含水酸化物のヒドロゾル又はヒドロゲル若しくはそれらの乾燥物に、焼成時の粒子成長を抑制する粒子成長抑制剤としてＰ、Ｓ、Ｍｏ、Ｗ、Ｖ、Ｂ、Ａｌ、及びＳｉから選ばれた１種又は２種以上の金属を含むオキシアニオン及び／又は金属カルボニルアニオン、又は、Ｆｅ、Ｎｉ、Ｃｏ、Ｍｇ、Ｍｎ、Ｐｔ、Ｐｄ、Ｒｈ、及びＲｕから選ばれた１種又は２種以上の金属カチオン、若しくは、これらオキシアニオン及び／又は金属カルボニルアニオンと金属カチオンとを添加したのち、乾燥、焼成することを特徴とする多孔質４族金属酸化物の製造方法である。
【００１２】
本発明の多孔質４族金属酸化物の製造方法において、アニオンの添加は４族金属酸化物の等電点未満のｐＨで、カチオンの添加は４族金属酸化物の等電点以上のｐＨで、アニオン及びカチオンを同時に添加する場合は４族金属酸化物の等電点未満のｐＨで行われることが好ましく、４族金属含水酸化物のヒドロゾル又はヒドロゲルは、４族金属含水酸化物の沈殿領域ｐＨと溶解領域ｐＨとの間を交互に複数回以上スイングすることにより製造することが好ましい。
【００１３】
本発明方法において、４族金属含水酸化物のヒドロゾル又はヒドロゲル又はその乾燥物は、ＭＯ2・ｎＨ2Ｏとして表される当該４族金属含水酸化物のｎが０．０２以上のものであればよい。ここで規定するｎが０．０２以上である意味は、４族金属含水酸化物のヒドロゾル又はヒドロゲル又はその乾燥物がもつＯＨ基の下限値を規定するものである。４族金属含水酸化物のヒドロゾル又はヒドロゲル又はその乾燥物が有するＯＨ基が熱履歴ではずれていくことでシンタリングや脱水縮合による粒子成長が起こる。この際、置換可能なＯＨ基を他の官能基等と置換することによって、熱安定性を増し、高比表面積を得ることができる。従って、従来より汎用されている加水分解法、中和反応法、ゾルゲル法等の方法で製造したものを用いることができる。また、制御されたシャープな細孔径分布を持ち、優れた反応活性・選択性を有する触媒を製造するのに好適な多孔質４族金属酸化物を得るために、４族金属含水酸化物のヒドロゾルあるいはヒドロゲル又はその乾燥物の製造を、ヒドロゾルのｐＨをその沈殿領域と溶解領域に交互に複数回以上スイングすることによって行うことができる。
【００１４】
ここで、４族金属含水酸化物のヒドロゾル又はヒドロゲル又はその乾燥物を製造するために用いる４族金属化合物としては、具体的には、チタン（Ti）、ジルコニウム（Zr）又はハフニウム（Hf）の塩化物、硝酸塩、硫酸塩、炭酸塩、酢酸塩、燐酸塩、ホウ酸塩、蓚酸塩、フッ酸塩、珪酸塩、ヨウ素酸塩等の４族金属塩や、チタン酸、ジルコニウム酸、ハフニウム酸等の４族金属オキソ酸塩等及び４族金属のアルコキシド類であり、これらの１種のみを単独で使用できるほか、２種以上の混合物として使用することもできる。これらの４族金属化合物のうち、チタンの場合に特に好ましいものとしては、例えば、四塩化チタン、硫酸チタン、硫酸チタニル、三塩化チタン、チタンメトキシド、チタンエトキシド、チタンプロポキシド、チタンイソプロポキシド、チタンブトキシド等を挙げることができる。また、ジルコニウムの場合に特に好ましいものとしては、例えば、四塩化ジルコニウム、オキシ塩化ジルコニウム、硫酸ジルコニウム、硝酸ジルコニウム、酢酸ジルコニウム、ジルコニウムアセチルアセナート、ジルコニウムプロポキシド、ジルコニウム t-ブトキシド等を挙げることができる。又はフニウムの場合に特に好ましいものとしては、例えば、塩化ハフニウム、硫酸ハフニウム、オキシ塩化ハフニウム等を挙げることができる。
【００１５】
また、本発明に用いる粒子成長抑制剤は、Ｐ、Ｓ、Ｍｏ、Ｗ、Ｖ、Ｂ、Ａｌ、Ｓｉ等から選択されるオキシアニオン、金属カルボニルアニオン、及びＦｅ、Ｎｉ、Ｃｏ、Ｍｇ、Ｍｎ、Ｐｔ、Ｐｄ、Ｒｈ、Ｒｕ等の金属カチオンを用いることができる。更に詳しくは、ＰＯ4 3-、ＮｂＯ4 3-、ＳＯ4 2-、ＭｏＯ4 2-、ＷＯ4 2-、ＣｒＯ4 2-、ＢＯ3 3-、ＡｌＯ3 3-、ＳｉＯ4 4-、ＧｅＯ4 4-等のイオンの形を有するオキシアニオン、金属カルボニルアニオンＦｅ2+、Ｆｅ3+、Ｎｉ2+、Ｃｏ2+、Ｃａ2+、Ｍｇ2+、Ｍｎ2+、Ｙ3+、Ｐｔ2+、Ｐｄ2+、Ｒｈ3+、Ｒｕ3+等の金属カチオンである。
【００１６】
特に好適なオキシアニオンを提供する化合物としては、モリブデン酸アンモニウム｛(NH4)6Mo7O24・4H2O、（NH4）2MoＯ4、(NH4)Mo2O7｝、モリブデン酸ソーダ(Na2MoＯ4・2H2O)、モリブデン酸（H2MoO4、H2MoO3・H2O）、五塩化モリブデン(MoCl5)、ケイモリブデン酸(H4SiMo12O40・nH2O)、タングステン酸（H2WO4）、タングステン酸アンモニウム｛5(NH4)2O・12WO3・H2O、3(NH4)2O・12WO3・nH2O｝、タングステン酸ナトリウム（Na2ＷO4・2H2O）、メタバナジン酸（HVO3）、オルトバナジン酸（H3VO4）、ピロバナジン酸（H2V2O7）、ペルオキソバナジン酸（HVO4）、ポリバナジウム酸、H2CrO4、クロム酸アンモニウム｛(NH4)2CrO4｝、H3PO4、HPO3、H4P2O7、P2O5、NH4H2PO4、(NH4)2HPO4、(NH4)3PO4・H2O、Nb2O5・nH2O、Ca3NbO4、Ca4Nb2O7、H3BO3、NH4B5O8、H2SO4、(NH4)2SO4、更にH3[PO4W12O36]・5H2OやMo、W、Vをポリ酸とするヘテロポリ酸塩等を挙げることができる。これらは、その１種のみを単独で使用できるほか、２種以上の混合物として使用することもできる。
【００１７】
また、金属カルボニルアニオンを供給する多価金属塩の好適な化合物としては、例えば(NEt4)[Mo(CO)5(OOCCH3)]、Mo(CO)6-NEt3-EtSH、Ru3(CO)12-NEt3-EtSH、(η-C5H4Me)2Mo2Co2S3(CO)4、W(CO)6、W(CO)6-NEt3-EtSH、Cr(CO)6-NEt3-EtSH等で表される金属カルボニルアニオンである。
【００１８】
また、多価金属カチオンを供給する多価金属塩の好適な化合物としては、二価以上の金属の塩をいい、例えば、硫酸第１鉄（FeSO4・H2O）、硫酸第２鉄｛４｛Fe2(SO4)3｝、塩化第１鉄、塩化第２鉄（FeCl3）、硝酸第１鉄、硝酸第２鉄｛Fe(NO3)3・9H2O｝、硝酸ニッケル｛Ni(NO3)2・6H2O｝、硫酸ニッケル（NiSO4・6H2O）、塩化ニッケル（NiCl2）、酢酸ニッケル｛Ni(CH3CO2)2・4H2O｝、酢酸コバルト｛Co(CH3CO2)2・4H2O｝、硝酸コバルト｛Co(NO3)2・6H2O｝、硫酸コバルト（CoSO4・7H2O）、塩化コバルト（CoCl2・6H2O）、硝酸カルシウム、硫酸カルシウム、塩化カルシウム、硝酸マグネシウム（Mg(NO3)2・6H2O）、硫酸マグネシウム（MgSO4・7H2O）、塩化マグネシウム（MgCl2・H2O）、炭酸マグネシウム（MgCO3）硝酸マンガン｛Mn(NO3)2｝、硫酸マンガン（MnSO4・7H2O）、塩化マンガン、燐酸マンガン（MnPO4）、炭酸マンガン（MnCO3）、硼酸マンガン（MnB4O7・8H2O）、硝酸イットリウム｛Y(NO3)3・6H2O｝、硫酸イットリウム｛Y(SO4)3・8H2O｝、炭酸イットリウム｛Y(CO3)3・3H2O｝、塩化イットリウム（YCl3・6H2O）、燐酸イットリウム（YPO4）、硝酸パラジウム（Pd(NO3)2）、硫酸パラジウム（PdSO4）、塩化パラジウム（PdCl2）、パラジウム塩化カルボニル｛Pd(CO)Cl｝等である。
【００１９】
本発明に用いる前記粒子成長抑制剤はその１種のみを単独で使用できるほか、２種以上の混合物として使用することもできる。
【００２０】
また、これら粒子成長抑制剤で水素化処理触媒活性を有するものとしては、Ｍｏ、Ｗ、Ｎｉ、Ｃｏ、Ｆｅ、Ｐ、Ｂ、Ｐｔ、Ｐｄ、Ｒｈ、Ｒｕが挙げられる。
【００２１】
また、ヒドロゾルのｐＨを沈殿領域と溶解領域の間を交互に複数回変動させるｐＨ調整剤として好適な化合物は、原料となる四塩化チタン、硫酸チタン、硫酸チタニル、四塩化チタン、三塩化チタン、硫酸第１鉄、硫酸第２鉄、塩化第１鉄、塩化第２鉄、硝酸第１鉄、硝酸第２鉄、硝酸ニッケル、硫酸ニッケル、塩化ニッケル、硝酸コバルト、硫酸コバルト、塩化コバルト、硝酸マンガン、硫酸マンガン、塩化マンガン、硝酸イットリウム、硫酸イットリウム、塩化イットリウムのほか硝酸（HNO3）、塩酸（HCl）、硫酸（H2SO4）、炭酸（H2CO3）、蟻酸（HCOOH）、酢酸（CH3COOH）等の酸と、アンモニア（NH3）、水酸化ナトリウム（NaOH）、水酸化カリウム（KOH）、炭酸ナトリウム（Na2CO3）、炭酸カリウム（K2CO3）、炭酸水素ナトリウム（NaHCO3）、炭酸水素カリウム（KHCO3）、炭酸水素ナトリウムカリウム（KNaCO3）等のアルカリを挙げることができる。また、これらはその１種のみを単独で使用できるほか、２種以上の混合物として使用することもできる。
【００２２】
［多孔質４族金属酸化物の製造方法］
（４族金属含水酸化物の製造）
４族金属含水酸化物のヒドロゾル、ヒドロゲル又はそれらの乾燥物で、ＭＯ2・ｎＨ2Ｏとして表される当該４族金属含水酸化物のｎが０．０２以上のものを製造する条件は、該多孔質４族金属酸化物（ＭＯ2）濃度は１〜２０重量％、好ましくは３〜１５重量％、反応温度は常温から３００℃、好ましくは常温から１８０℃、更に好ましくは常温から１００℃、反応圧力は常圧から３．０ＭＰａで、好ましくは常圧から０．９ＭＰａで、更に好ましくは常圧から０．１ＭＰａ、ｐＨは０．５〜１１、好ましくは１．０〜１０の範囲でアルカリによる中和反応あるいは加水分解反応によって４族金属含水酸化物を生成する。
【００２３】
（粒子成長抑制剤の添加）
上記一般式ＭＯ2・ｎＨ2Ｏ（但し、Ｍは４族金属を示し、ｎは０．０２以上である）で表される４族金属含水酸化物のヒドロゾル又はヒドロゲル若しくはそれらの乾燥物に、粒子成長抑制剤として１種又は２種以上のアニオン、又はカチオン、若しくはこれらアニオン及びカチオンを添加するが、この際に、粒子成長抑制剤がアニオンの場合には好ましくは４族金属酸化物の等電点未満のｐＨで添加するのがよく、また、粒子成長抑制剤がカチオンの場合には好ましくは４族金属酸化物の等電点以上のｐＨで添加するのがよく、更に、粒子成長抑制剤がアニオン及びカチオンの場合には好ましくは４族金属酸化物の等電点未満のｐＨで同時に添加するのがよい。これは、イオン交換等による置換がより効果的に進むことによる。そして、これら粒子成長抑制剤の添加量については、４族金属酸化物１００ｇ当たり０．０６〜６ｇ当量、好ましくは０．１〜５ｇ当量添加し、温度常温から１００℃で、熟成時間０．１〜５時間、好ましくは０．２〜３時間保持する。
なお、上記ヒドロゾルはその生成段階のもの、ヒドロゲルはその生成後のものに粒子成長抑制剤を添加するのが効果的である。
【００２４】
例えば、酸化チタンの場合は、含水酸化チタンを洗浄し、粒子成長抑制剤として酸化チタンのアナターゼの等電点である６．１未満でのｐＨで一種類以上のアニオンを添加あるいは等電点以上のｐＨで一種類以上のカチオンを添加、アニオンとカチオンを同時に添加する場合は等電点未満のｐＨで、酸化チタン１００g当たり０．０６〜６ｇ当量、好ましくは０．１〜５ｇ当量添加し、常温から１００℃で、熟成時間０．１〜５時間、好ましくは０．２〜３時間保持する。
【００２５】
また、粒子成長抑制剤の添加法としては、直接混練法も使用することができる。この方法においては、粒子成長抑制剤をゲルあるいは乾燥物に４族金属酸化物１００g当たり０．０５〜５ｇ当量、好ましくは０．１〜４ｇ当量粒子成長抑制剤を直接添加し、常温から１００℃の温度範囲で、熟成時間０．１〜５時間、好ましくは０．２〜３時間混練する。
【００２６】
（乾燥・焼成条件）
４族金属酸化物基準での含水量を３０〜９００重量％、好ましくは５０〜７００重量％にろ過・脱水し、所要の形状に成型し、乾燥温度４０〜350℃、好ましくは８０〜２００℃で、乾燥時間０．５〜２４時間、好ましくは８０〜２００℃で乾燥し、温度３５０〜１２００℃、好ましくは４００〜７００℃で焼成する。
【００２７】
また、種子生成工程とヒドロゾル合成工程とを有する４族金属含水酸化物のヒドロゾルの製造方法については、具体的には特公昭６０−５０,７２１号公報に記載された方法を例示することができる。
すなわち、種子生成工程については、不均一沈殿法、均一沈殿法、共沈法、イオン交換法、加水分解法、及び金属溶解法等の慣用の方法を採用することができる。また、ヒドロゾル合成工程については、上記種子生成工程で得られた４族金属含水酸化物のヒドロゾルに４族金属化合物の水溶液、及び／又はｐＨ調整剤とを交互に添加し、ヒドロゾル溶解ｐＨ領域とヒドロゾル析出ｐＨ領域との間を交互に複数回変動させるものであり、ヒドロゾル溶解ｐＨ領域とは微細粒子のヒドロゾルを可溶化し得るｐＨ領域をいい、また、ヒドロゾル析出ｐＨ領域とはヒドロゾル粒子の成長及び凝集を生起させるｐＨ領域をいう。更に、このヒドロゾル合成工程においては、必要により、熟成、洗浄、固形分含量調節等の処理が行われ、所望の性状を有する４族金属含水酸化物のヒドロゾルあるいはヒドロゲルとされる。
【００２８】
上記４族金属酸化物の製造において、該４族金属含水酸化物の製造条件は、ｐＨをスイングする各段階の沈殿領域のｐＨを０．５〜１１、濃度を０．１〜２０重量％、温度を常温から３００℃、保持時間を０．０１〜０．5時間、好ましくは０．０２〜０．３時間とする。また、４族金属含水酸化物の溶解領域のｐＨは０〜３、濃度は０．１〜２０重量％、温度は常温から３００℃、保持時間は０．０２〜５時間の範囲が好適である。また、沈殿領域と溶解領域に交互に保持する回数は２回から２０回の範囲が好適である。
【００２９】
例えば、酸化チタンの場合は、該含水酸化チタンのｐＨをスイングする各段階の製造条件は、沈殿領域のｐＨを１．０〜１０、濃度を０．１〜１５重量％、温度を常温から１８０℃、保持時間を０．０１〜０．5時間、好ましくは０．０２〜０．３時間、溶解領域のｐＨを０〜２、濃度を０．１〜１５重量％、温度を常温から１８０℃、保持時間を０．０２〜５時間の範囲が好適である。また、沈殿領域と溶解領域に交互に保持する回数は２回から１０回の範囲が好適である。
【００３０】
本発明方法により得られた多孔質４族金属酸化物は、触媒担体、触媒、乾燥剤、吸着剤、充填剤等の用途に有用であるが、特に、本発明方法により得られた多孔質４族金属酸化物は、８０ｍ2／ｇ以上の高比表面積を持ち、細孔シャープネス度（定義を後述）が３０％以上等の特徴を持つため水素化処理（脱硫、脱窒素、脱メタル、アスファルテン分解、芳香族の水素化）、水素化分解、アルキレーション、フィッシャートロプシュ、排煙脱硝、光反応等の高性能触媒担体又は触媒として使用することができる。なお、８０ｍ2／ｇ以下の高比表面積では、所望の反応活性を発揮しにくくなる。また、細孔シャープネス度が３０％以下であると反応の選択性が低下することになる。
【００３１】
［物理性状の測定について］
（細孔シャープネス度）
水銀ポロシメータにより測定された累積細孔分布曲線に関し、先ず累積細孔容積を示す縦軸と細孔直径（Å）を表す横軸において、全細孔容積（PVT）の（１／２）ＰＶにおける細孔径（メデアン直径）を求める。次に、メディアン直径の対数値における±５％の細孔径範囲内に有する細孔容積（PVM）を求め、その細孔容積（PVM）と全細孔容積（PVT）から以下の式により、細孔分布のシャープ度を表わす細孔シャープネス度を求める。
細孔シャープネス度＝｛細孔容積（PVM）／全細孔容積（PVT）｝*１００
ここで定義する細孔シャープネス度は、全細孔容積に対する反応に最適な細孔の度合いを評価するための因子であり、細孔シャープネス度が大きい程、シャープな細孔分布を有することになり、好ましいものとなる。
【００３２】
（比表面積の測定法）
触媒及び担体の比表面積は、ＢＥＴの三点法により測定し、測定機器にはマウンテック社製Macsorb Model-1201を使用した。
【００３３】
（細孔分布の測定法）
触媒及び担体の細孔容積と細孔分布は、測定圧力４１４ＭＰａで水銀圧入法により測定し、測定機器には島津製作所製オートポア9200形を使用した。
【００３４】
（結晶構造の測定法）
触媒及び担体の結晶構造はX線回折法により測定し、測定機器にはPHILIPS社製PW3710を使用した。
【００３５】
【発明の実施の形態】
以下、実施例及び比較例に基づいて、本発明の好適な実施の形態を具体的に説明する。
【００３６】
実施例１
［ヒドロゾルの調製］
（四塩化チタン水溶液の調製）
氷を加えた純水に冷却した四塩化チタン（TiCl4）１ｋｇを徐々に添加し酸化チタン換算濃度２１０ｇ／リットルの四塩化チタン水溶液を調製した。
（14wt%ＮＨ4ＯＨ水溶液の調製）
28wt%ＮＨ4ＯＨを２倍に希釈し、14wt%ＮＨ4ＯＨ水溶液を調製した。
【００３７】
（ヒドロゾル合成工程）
次に、３０リットルの撹拌機付きベッセルに純水１０リットルを入れ、攪拌しながら前記四塩化チタン水溶液１．５リットルを添加し、ｐＨを０．５以下まで低下させた。
この溶液に上記14wt%ＮＨ4ＯＨ水溶液２．３リットルを添加し、ｐＨを７まで上昇させ、約５分間放置した。
【００３８】
（濾過、洗浄）
上記ヒドロゾル合成工程終了後、濾過し、得られたケーキを純水にて洗浄し、硝酸銀滴定により濾液中に塩素（Cl-）が確認されなくなるまで洗浄操作を繰り返し、チタニアヒドロゾルを得た。
【００３９】
（乾燥物の調製）
以上のようにして得られたチタニアヒドロゾルを吸引濾過し、含水量約５０重量％になるまで脱水し、次いで穴径１．５ｍｍφのダイスを用いて成形し、得られた成形物を１２０℃にて３時間乾燥し、チタニア乾燥成形物を得た。
【００４０】
（粒子成長抑制剤添加工程）
上記で得られたチタニア乾燥成型物を、酸化チタン当たり酸化物基準で１６．３重量％のパラモリブデン酸アンモニウムを含有する水溶液に浸漬し、室温下に２時間放置したのち、５Ｃの濾紙で濾過し、モリブデン担持物を得た。
【００４１】
（乾燥焼成工程）
得られたモリブデン担持物を１２０℃で３時間乾燥した後、５００℃で３時間焼成し、モリブデン担持チタニア触媒を得た。
得られたモリブデン担持チタニア触媒の物性を表１に示す。
【００４２】
実施例２
実施例１と同じ方法でヒドロゾルを合成し、更に撹拌しながら前記四塩化チタン水溶液１．５リットルを添加してｐＨを再び０．５まで低下させ、次いで５分間放置した後、14wt%ＮＨ4ＯＨ水溶液２．８リットルを添加して再びｐＨを７まで上昇させ、更に５分間放置した。
これらの操作を更に３回繰り返し、ヒドロゾル溶解ｐＨ領域（ｐＨ０．５）とヒドロゾル析出ｐＨ領域（ｐＨ７）との間を交互に合計５回変動させた。
これ以降の洗浄・濾過・成形・乾燥・粒子成長抑制剤添加工程・乾燥焼成工程は実施例１と同様とした。
得られたモリブデン担持チタニア触媒の物性を表１に示す。
【００４３】
実施例３
粒子成長抑制剤として、酸化チタン当たり酸化物基準で８重量％の燐酸を用いた以外は、実施例２と同様にしてリン担持チタニア触媒を得た。
得られた触媒の物性を表１に示す。
【００４４】
【表１】
実施例４
実施例２の洗浄後のヒドロゾルを、酸化チタン当たり酸化物基準で１６．３重量％のパラモリブデン酸アンモニウムを含有する水溶液に浸漬し、室温下に２時間放置した後、吸引濾過し、含水量５０重量％になるまで脱水した。次いで、穴径１．５ｍｍφのダイスを用いて成形し、得られた成形物を１２０℃で３時間乾燥した後、５００℃で３時間焼成してモリブデン担持チタニア触媒を得た。
得られた触媒の物性を表２に示す。
【００４６】
実施例５
実施例２の濾過後のヒドロゲルを、酸化チタン当たり酸化物基準で８重量％の燐酸を含有する水溶液に浸漬し、室温下に２時間放置した後、吸引濾過し、含水量５０重量％になるまで脱水した。次いで、穴径１．５ｍｍφのダイスを用いて成形し、得られた成形物を１２０℃で３時間乾燥した後、５００℃で３時間焼成してリン担持チタニア触媒を得た。
得られた触媒の物性を表２に示す。
【００４７】
実施例６
粒子成長抑制剤として、酸化チタン当たり酸化物基準で２０．６重量％のメタタングステン酸アンモニウムを用いた以外は、実施例４と同様にしてタングステン担持チタニア触媒を得た。
得られた触媒の物性を表２に示す。
【００４８】
【表２】
実施例７
実施例５と同様の方法で原料を硫酸チタンにした濾過後のヒドロゲルに、粒子成長抑制剤として硫酸を、酸化チタン当たりＳＯ3基準で９重量％加えた以外は、実施例５と同様にして硫酸担持チタニア触媒を得た。
得られた触媒の物性を表３に示す。
【００５０】
実施例８
粒子成長抑制剤として、酸化チタン当たり酸化物基準で３．９重量％の硼酸を用いた以外は、実施例４と同様にしてボリア担持チタニア触媒を得た。
得られた触媒の物性を表３に示す。
【００５１】
実施例９
粒子成長抑制剤として、酸化チタン当たり金属酸化物基準で９．０重量％の硫酸第１鉄を用いた以外は、実施例５と同様にして鉄担持チタニア触媒を得た。
得られた触媒の物性を表３に示す。
【００５２】
【表３】
実施例１０
粒子成長抑制剤として、酸化チタン当たり酸化物基準で８．４重量％の硝酸ニッケルを用いた以外は、実施例５と同様にしてニッケル担持チタニア触媒を得た。
得られた触媒の物性を表４に示す。
【００５４】
実施例１１
粒子成長抑制剤として、酸化チタン当たり酸化物基準で３．０重量％の燐酸と１０．０重量％のパラモリブデン酸アンモニウムを同時に用いた以外は、実施例５と同様にしてリン・モリブデン担持チタニア触媒を得た。
得られた触媒の物性を表４に示す。
【００５５】
実施例１２
粒子成長抑制剤として、酸化チタン当たり酸化物基準で３．０重量％の硝酸コバルトと１０．０重量％のパラモリブデン酸アンモニウムを同時に用いた以外は、実施例４と同様にしてコバルト・モリブデン担持チタニア触媒を得た。
得られた触媒の物性を表４に示す。
【００５６】
【表４】
実施例１３
粒子成長抑制剤として、酸化チタン当たり酸化物基準で３．０重量％の硝酸ニッケルと１０．０重量％のパラモリブデン酸アンモニウムを同時に用いた以外は、実施例４と同様にしてニッケル・モリブデン担持チタニア触媒を得た。
得られた触媒の物性を表５に示す。
【００５８】
実施例１４
粒子成長抑制剤として、酸化チタン当たり酸化物基準で２．０重量％の燐酸と８．０重量％のパラモリブデン酸アンモニウムと２．０重量％の硝酸コバルトを同時に用いた以外は、実施例５と同様にしてリン・モリブデン・コバルト担持チタニア触媒を得た。
得られた触媒の物性を表５に示す。
【００５９】
実施例１５
粒子成長抑制剤として、酸化チタン当たり酸化物基準で２．０重量％の燐酸と８．０重量％のパラモリブデン酸アンモニウムと２．０重量％の硝酸ニッケルとを同時に用いた以外は、実施例５と同様にしてリン・モリブデン・ニッケル担持チタニア触媒を得た。
得られた触媒の物性を表５に示す。
【００６０】
【表５】
実施例１６
粒子成長抑制剤として、酸化チタン当たり酸化物基準で２．０重量％の硝酸ニッケルと８．０重量％のパラモリブデン酸アンモニウムと２．０重量％の硝酸コバルトとを同時に用いた以外は、実施例５と同様にしてニッケル・モリブデン・コバルト担持チタニア触媒を得た。
得られた触媒の物性を表６に示す。
【００６２】
実施例１７
粒子成長抑制剤として、酸化チタン当たりＳＯ3基準で５重量％の硫酸と金属酸化物基準で８．０重量％のパラモリブデン酸アンモニウムと金属酸化物基準で２．０重量％の硝酸ニッケルとを用いた以外は、実施例７と同様にして硫酸・モリブデン・ニッケル担持チタニア触媒を得た。
得られた触媒の物性を表６に示す。
【００６３】
実施例１８
粒子成長抑制剤として、酸化チタン当たり酸化物基準で２．０重量％の燐酸と８．０重量％のメタタングステン酸アンモニウムと２．０重量％の硝酸ニッケルとを同時に用いた以外は、実施例４と同様にしてリン・タングステン・ニッケル担持チタニア触媒を得た。
得られた触媒の物性を表６に示す。
【００６４】
【表６】
実施例１９
粒子成長抑制剤の添加方法を浸漬からポアフィリング法による含浸に変えた以外は、実施例３と同様にしてリン担持チタニア触媒を得た。
得られた触媒の物性を表７に示す。
【００６６】
実施例２０
粒子成長抑制剤の添加方法を浸漬から直接混練に変えた以外は、実施例５と同様にしてリン担持チタニア触媒を得た。
得られた触媒の物性を表７に示す。
【００６７】
実施例２１
粒子成長抑制剤として、酸化チタン当たり酸化物基準で８重量％の燐酸を用いた以外は、実施例４と同様にしてリン担持チタニア触媒を得た。
得られた触媒の物性を表７に示す。
【００６８】
【表７】
実施例２２
粒子成長抑制剤として、酸化チタン当たり酸化物基準で３０．３重量％のパラモリブデン酸アンモニウムを用いた以外は、実施例４と同様にしてモリブデン担持チタニア触媒を得た。
得られた触媒の物性を表８に示す。
【００７０】
実施例２３
焼成温度を３５０℃に変えた以外は、実施例５と同様にしてリン担持チタニア触媒を得た。
得られた触媒の物性を表８に示す。
【００７１】
実施例２４
粒子成長抑制剤として、酸化チタン当たり酸化物基準で１６．３重量％のパラモリブデン酸アンモニウムを用いて、焼成温度を６００℃に変えた以外は、実施例５と同様にしてモリブデン担持チタニア触媒を得た。
得られた触媒の物性を表８に示す。
【００７２】
【表８】
実施例２５
焼成温度を２００℃に変えた以外は、実施例５と同様にしてリン担持チタニア触媒を得た。
得られた触媒の物性を表９に示す。
【００７４】
実施例２６
実施例２４のゾル合成温度条件を９５℃に変えた以外は、実施例２４と同様にしてモリブデン担持チタニア触媒を得た。
得られた触媒の物性を表９に示す。
【００７５】
実施例２７
実施例２４のゾル合成温度条件を２００℃に変えた以外は、実施例２４と同様にしてモリブデン担持チタニア触媒を得た。
得られた触媒の物性を表９に示す。
【００７６】
実施例２８
実施例２と同様の方法で原料をオキシ塩化ジルコニウムにした濾過後のジルコニアヒドロゲルを、酸化ジルコニウム当たり酸化物基準で１６．３重量％のパラモリブデン酸アンモニウムを含有する水溶液に浸漬し、室温下に２時間放置した後、吸引濾過し、含水量５０重量％になるまで脱水した。次いで、穴径１．５ｍｍφのダイスを用いて成形し、得られた成形物を１２０℃で３時間乾燥した後、５００℃で３時間焼成してモリブデン担持ジルコニア触媒を得た。
得られた触媒の物性を表９に示す。
【００７７】
【表９】
比較例１
四塩化チタン水溶液と14wt%ＮＨ4ＯＨ水溶液を９５℃の合成温度条件にて連続で混合し、チタニアヒドロゾルを得た。得られたチタニアヒドロゾルを濾過し、水で３回洗浄し、次いで成形した後、５００℃で３時間焼成してチタニア担体を製造した。
得られたチタニア担体の物性を表１０に示す。
【００７９】
比較例２
実施例２で得られた粒子成長抑制剤添加前のチタニア成形乾燥物を５００℃で焼成し、チタニア担体を製造した。
得られたチタニア担体の物性を表１０に示す。
【００８０】
比較例３
実施例２で得られた粒子成長抑制剤添加前のチタニア成形物を３７０℃で乾燥し、含水酸化物水分量（ｎ）を０．０１に調整したのち、粒子成長抑制剤として、酸化チタン当たり酸化物基準で１６．３重量％のパラモリブデン酸アンモニウムを加えた以外は実施例２と同様にしてモリブデン担持チタニア触媒を得た。
得られた触媒の物性を表１０に示す。
【００８１】
【表１０】
実施例２９
小型の流通式反応装置を用いて、減圧軽油（窒素濃度０．２重量％）を原料とし、反応温度３７０℃、反応圧力（水素分圧）８．０ＭＰａ、ＬＨＳＶ２-1、Ｈ2／oil比５００Ｎｍ3／Ｋｌの反応条件で、触媒として実施例１５のリン・モリブデン・ニッケル担持チタニア触媒（ＢＥＴ比表面積は１６７ｍ2／ｇ）を用いて水素化処理を行った。得られた生成油の窒素濃度は０．０２２重量％であった。
【００８３】
比較例４
触媒として市販のチタニアを触媒化し、ＢＥＴ比表面積４２ｍ2／ｇのＮｉ／Ｍｏ担持チタニア触媒（Ｎｉ:2.4wt%／Ｍｏ:16.7wt%）を用いた以外は、上記実施例２９と同様にして水素化処理を行った。この水素化処理の結果、生成油の窒素濃度は０．１０重量％となった。
脱窒素反応を１次反応として脱窒素反応速度を求めると、実施例１５の触媒は、比較例４の触媒と比較して、約３．５倍の脱窒素活性を示した。
【００８４】
実施例３０
小型の流通式反応装置を用いて、常圧軽油（硫黄濃度１．３重量％）を原料とし、反応温度３５０℃、反応圧力（水素分圧）５．０ＭＰａ、ＬＨＳＶ２-1、Ｈ2／oil比２００Ｎｍ3／Ｋｌの反応条件で、触媒として実施例１４のリン・モリブデン・コバルト担持チタニア触媒（ＢＥＴ比表面積は１４９ｍ2／ｇ）を用いて水素化処理を行った。得られた生成油の硫黄濃度は８０ｐｐｍであった。
【００８５】
比較例５
触媒として、市販のチタニアを触媒化し、ＢＥＴ比表面積４０ｍ2／ｇのＣｏ・Ｍｏ担持チタニア触媒（Ｃｏ:3.9wt%／Ｍｏ:13.3wt%）を用いた以外は、上記実施例３０と同様にして水素化処理を行った。この水素化処理の結果、生成油の硫黄濃度は４５０ｐｐｍとなった。
脱硫反応を１．５次反応として脱硫反応速度を求めると、実施例１４の触媒は、比較例５の触媒と比較して、約３．８倍の脱硫活性を示した。
【００８６】
【発明の効果】
本発明によれば、単に比表面積が大きいだけでなく、同時に熱安定性にも優れた多孔質４族金属酸化物を容易に製造することができる。また、制御されたシャープな細孔径分布を有する４族金属含水酸化物のヒドロゾルを用いることにより、優れた反応選択性を有し、しかも、比表面積が大きくて触媒活性に優れているだけでなく、同時に熱安定性にも優れており、４族金属の触媒又は触媒担体として有用な多孔質４族金属酸化物を容易に製造することができる。
【図面の簡単な説明】
【図１】 図１は、比較例２の熱処理温度と比表面積の関係を示すグラフ図である。
【図２】 図２は、実施例２３の焼成時間と比表面積の関係を示すグラフ図である。
【図３】 図３は、比較例と実施例の焼成物のＸ線回折図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a porous Group 4 metal oxide useful for uses such as a catalyst carrier, a catalyst, a desiccant, an adsorbent, and a filler, a method for producing them, and the use thereof. TECHNICAL FIELD The present invention relates to a porous group 4 metal oxide hydrotreating catalyst carrier and catalyst having a high surface area and excellent thermal stability, a production method thereof, and use thereof.
[0002]
[Prior art]
Conventionally, the porous Group 4 metal oxide is, for example, a method of hydrolyzing a titanium sulfate (titanyl sulfate) solution, which is a general method for synthesizing titanium hydroxide in a liquid phase, titanium tetrachloride or titanium sulfate (titanyl sulfate). It is manufactured by drying and firing a Group 4 metal hydroxide produced by a method of neutralizing an aqueous solution such as alkali with a sol / gelation method of hydrolyzing titanium alkoxide.
[0003]
However, the titania produced by such a conventional method has poor thermal stability, and as the firing temperature increases, as shown in the relationship between the specific surface area and the firing temperature in FIG. It was difficult to maintain a high specific surface area. This is because particle growth occurs by so-called sintering or dehydration condensation during the high-temperature firing. For example, in the case of hydrous titanium oxide, crystallization or crystal transition from amorphous to anatase or rutile occurs due to sintering or dehydration condensation, and the specific surface area is drastically reduced as shown in FIG.
[0004]
For this reason, for example, a titania support or a titania catalyst produced by a conventional technique is excellent in hydrotreating activity per unit specific surface area as a hydrocarbon hydrotreating catalyst, but is not limited to alumina or silica. It was not used industrially like the catalyst support or catalyst of the system. In addition, for example, when used as an alkylation catalyst, it is necessary to perform a high temperature treatment in order to develop the acidity as a super strong acid, but the conventional support has poor thermal stability and a low specific surface area. The absolute amount of the acid decreased, and the required performance as a catalyst could not be ensured. Also, when used as a catalyst for flue gas denitration, it is usually 40 to 50 m due to the problem of thermal stability, despite its excellent denitration activity per unit specific surface area.2Since it can be used only with a low specific surface area of / g, a large amount of catalyst is required at present. Further, there is a problem that the temperature range of application is narrow due to the problem of thermal stability. In addition, titania has a high wear strength, but when used as a Fischer-Tropsch (FT) reaction catalyst, only a low specific surface area can be obtained. The current situation is not. For this reason, the titania carrier and catalyst produced by the prior art cannot sufficiently satisfy the performance required depending on the purpose of use and conditions of use. That is, since the thermal stability is poor, a high specific surface area cannot be maintained at a high temperature, resulting in poor performance.
[0005]
In addition, it has been difficult to produce titania having a sharp pore size distribution by the conventional method described above. In general, it is necessary to control the pore diameter range of a catalyst having high performance to a pore diameter suitable for the target reactant. That is, it is important that there is no diffusion resistance of the reactants and that there are no small or too large useless pores that are not effective for the reaction. Therefore, it is ideal that the catalyst has a pore diameter controlled according to the purpose of the reaction. For example, the effective catalyst pore diameter for the reaction is 6 to 10 nm for the purpose of desulfurization of light oil, and 8 to 15 nm for the purpose of desulfurization of heavy oil. In the case of deasphaltening, it is in the range of 20 to 40 nm. However, the titania catalyst produced by the conventional method has a problem that sufficient performance cannot be obtained in terms of reaction selectivity, activity, and catalyst life because the catalyst pore diameter optimum for the reaction is small. .
[0006]
Therefore, as a method for solving such problems and sharpening the pore size distribution and controlling the range of the pore size, for example, in Japanese Patent Publication No. 60-50,721, a process of obtaining a seed hydrosol, The step of alternately changing the pH of the hydrosol between the hydrosol dissolution region and the hydrosol precipitation region to obtain a hydrosol in which crystals are grown to form loose aggregates, and the hydrosol that has formed the coarse aggregates is dried. And the manufacturing method of the porous inorganic oxide which has the process of baking and obtaining a metal oxide is proposed.
[0007]
However, this method alone can, for example, have a sharp pore size distribution controlled for titania, but does not cause a decrease in activity even with respect to thermal history due to catalyst firing or reaction heat in the reaction system. It has been difficult to produce such a titania catalyst.
[0008]
[Problems to be solved by the invention]
Therefore, the present inventors have conducted extensive studies on a porous Group 4 metal oxide having excellent thermal stability and a large specific surface area and a method for producing the same, and as a result, the general formula MO2・ NH2In the hydrosol or hydrogel of a Group 4 metal-containing oxide represented by O (wherein M represents a Group 4 metal and n is 0.02 or more), one kind as a particle growth inhibitor or After adding two or more types of anions, or cations, or these anions and cations, drying and firing, excellent thermal stability, 80 m2The present inventors have found that a porous group 4 metal oxide having a high specific surface area of at least / g and having a highly dispersed catalyst metal can be obtained.
[0009]
Accordingly, an object of the present invention is to provide a porous group 4 metal oxide having excellent thermal stability, a large specific surface area, and a highly dispersed catalyst metal, a method for producing the same, and a use thereof.
[0010]
Another object of the present invention is a catalyst or catalyst support having excellent thermal selectivity, a large specific surface area, high dispersion of catalyst metal, controlled sharp pore size distribution, and excellent reaction selectivity. It is an object to provide a porous group 4 metal oxide useful as a method, a production method thereof, and a use thereof.
[0011]
[Means for Solving the Problems]
That is, the present invention relates to the general formula MO2・ NH2In a hydrosol or hydrogel of a Group 4 metal-containing oxide represented by O (where M represents a Group 4 metal and n is 0.02 or more),Suppress particle growth during firingAs a particle growth inhibitorOxy anion and / or metal carbonyl anion containing one or more metals selected from P, S, Mo, W, V, B, Al, and Si, or Fe, Ni, Co, Mg, Mn , Pt, Pd, Rh, and Ru, or one or more metal cations, or these oxyanions and / or metal carbonyl anions and metal cations.After adding, drying and bakingFor producing a porous Group 4 metal oxideIt is.
[0012]
In the method for producing a porous Group 4 metal oxide of the present invention, the addition of an anion is at a pH below the isoelectric point of the Group 4 metal oxide, and the addition of a cation is at a pH above the isoelectric point of the Group 4 metal oxide. When an anion and a cation are added simultaneously, it is preferably carried out at a pH lower than the isoelectric point of the group 4 metal oxide. The hydrosol or hydrogel of the group 4 metal hydroxide is a precipitation region of the group 4 metal hydroxide. It is preferable to produce by swinging alternately between the pH and the dissolution region pH a plurality of times.
[0013]
In the method of the present invention, the hydrosol or hydrogel of a Group 4 metal-containing oxide or a dried product thereof is MO.2・ NH2The n of the said group 4 metal hydrous oxide represented as O should just be 0.02 or more. The meaning that n defined here is 0.02 or more defines the lower limit value of the OH group possessed by the hydrosol or hydrogel of the Group 4 metal-containing oxide or its dried product. When the OH group of the hydrosol or hydrogel of the Group 4 metal hydrated oxide or the dried product thereof is shifted by the thermal history, particle growth occurs due to sintering or dehydration condensation. At this time, by substituting the substitutable OH group with another functional group or the like, the thermal stability can be increased and a high specific surface area can be obtained. Therefore, what was manufactured by methods, such as a conventionally used hydrolysis method, neutralization reaction method, sol gel method, can be used. In addition, in order to obtain a porous Group 4 metal oxide suitable for producing a catalyst having a controlled and sharp pore size distribution and having excellent reaction activity and selectivity, a hydrosol of Group 4 metal hydrous oxide is obtained. Alternatively, the production of the hydrogel or dried product thereof can be carried out by swinging the pH of the hydrosol alternately several times or more between the precipitation region and the dissolution region.
[0014]
Here, as a Group 4 metal compound used for producing a hydrosol or hydrogel of a Group 4 metal-containing oxide or a dried product thereof, specifically, titanium (Ti), zirconium (Zr) or hafnium (Hf) is used. Group 4 metal salts such as chloride, nitrate, sulfate, carbonate, acetate, phosphate, borate, oxalate, hydrofluorate, silicate, iodate, titanic acid, zirconium acid, hafnium acid Group 4 metal oxoacid salts and the like and Group 4 metal alkoxides, and only one of them can be used alone, or a mixture of two or more can also be used. Among these group 4 metal compounds, particularly preferred in the case of titanium are, for example, titanium tetrachloride, titanium sulfate, titanyl sulfate, titanium trichloride, titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxy. And titanium butoxide. Particularly preferable examples of zirconium include zirconium tetrachloride, zirconium oxychloride, zirconium sulfate, zirconium nitrate, zirconium acetate, zirconium acetyl acetonate, zirconium propoxide, zirconium t-butoxide, and the like. . In the case of funium, particularly preferable examples include hafnium chloride, hafnium sulfate, hafnium oxychloride and the like.
[0015]
Further, the particle growth inhibitor used in the present invention is an oxyanion selected from P, S, Mo, W, V, B, Al, Si and the like, a metal carbonyl anion, and Fe, Ni, Co, Mg, Mn, Metal cations such as Pt, Pd, Rh, and Ru can be used. In more detail, POFour 3-, NbOFour 3-, SOFour 2-, MoOFour 2-, WOFour 2-, CrOFour 2-, BOThree 3-AlOThree 3-, SiOFour Four-, GeOFour Four-Oxyanions having the form of ions such as metal carbonyl anions Fe2+, Fe3+, Ni2+, Co2+, Ca2+, Mg2+, Mn2+, Y3+, Pt2+, Pd2+, Rh3+, Ru3+A metal cation.
[0016]
Compounds that provide particularly suitable oxyanions include ammonium molybdate {(NHFour)6Mo7Otwenty four・ 4H2O, (NHFour)2MoOFour, (NHFour) Mo2O7}, Sodium molybdate (Na2MoOFour・ 2H2O), molybdic acid (H2MoOFour, H2MoOThree・ H2O), molybdenum pentachloride (MoClFive), Silicomolybdic acid (HFourSiMo12O40・ NH2O), tungstic acid (H2WOFour), Ammonium tungstate {5 (NHFour)2O ・ 12WOThree・ H2O, 3 (NHFour)2O ・ 12WOThree・ NH2O}, sodium tungstate (Na2WOFour・ 2H2O), metavanadate (HVOThree), Orthovanadate (HThreeVOFour), Pyrovanadic acid (H2V2O7), Peroxovanadate (HVOFour), Polyvanadate, H2CrOFour, Ammonium chromate {(NHFour)2CrOFour}, HThreePOFour, HPOThree, HFourP2O7, P2OFive, NHFourH2POFour, (NHFour)2HPOFour, (NHFour)ThreePOFour・ H2O, Nb2OFive・ NH2O, CaThreeNbOFour, CaFourNb2O7, HThreeBOThree, NHFourBFiveO8, H2SOFour, (NHFour)2SOFourAnd further HThree[POFourW12O36] ・ 5H2Examples include heteropolyacid salts using O, Mo, W, and V as polyacids. These can be used alone or in a mixture of two or more.
[0017]
Further, as a suitable compound of a polyvalent metal salt that supplies a metal carbonyl anion, for example, (NEtFour) [Mo (CO)Five(OOCCHThree)], Mo (CO)6-NEtThree-EtSH, RuThree(CO)12-NEtThree-EtSH, (η-CFiveHFourMe)2Mo2Co2SThree(CO)Four, W (CO)6, W (CO)6-NEtThree-EtSH, Cr (CO)6-NEtThreeIt is a metal carbonyl anion represented by -EtSH or the like.
[0018]
Moreover, as a suitable compound of the polyvalent metal salt for supplying the polyvalent metal cation, a salt of a metal having a valence of 2 or more is used. For example, ferrous sulfate (FeSOFour・ H2O), ferric sulfate {4 {Fe2(SOFour)Three}, Ferrous chloride, ferric chloride (FeClThree), Ferrous nitrate, ferric nitrate {Fe (NOThree)Three・ 9H2O}, nickel nitrate {Ni (NOThree)2・ 6H2O}, nickel sulfate (NiSOFour・ 6H2O), nickel chloride (NiCl2), Nickel acetate {Ni (CHThreeCO2)2・ 4H2O}, cobalt acetate {Co (CHThreeCO2)2・ 4H2O}, cobalt nitrate {Co (NOThree)2・ 6H2O}, cobalt sulfate (CoSOFour・ 7H2O), cobalt chloride (CoCl2・ 6H2O), calcium nitrate, calcium sulfate, calcium chloride, magnesium nitrate (Mg (NOThree)2・ 6H2O), magnesium sulfate (MgSOFour・ 7H2O), magnesium chloride (MgCl2・ H2O), magnesium carbonate (MgCOThree) Manganese nitrate {Mn (NOThree)2}, Manganese sulfate (MnSOFour・ 7H2O), manganese chloride, manganese phosphate (MnPOFour), Manganese carbonate (MnCOThree), Manganese borate (MnBFourO7・ 8H2O), Yttrium nitrate {Y (NOThree)Three・ 6H2O}, yttrium sulfate {Y (SOFour)Three・ 8H2O}, Yttrium carbonate {Y (COThree)Three・ 3H2O}, Yttrium chloride (YClThree・ 6H2O), Yttrium phosphate (YPOFour), Palladium nitrate (Pd (NOThree)2), Palladium sulfate (PdSOFour), Palladium chloride (PdCl2), Palladium carbonyl chloride {Pd (CO) Cl}, and the like.
[0019]
The particle growth inhibitor used in the present invention can be used alone or in a mixture of two or more.
[0020]
Examples of these particle growth inhibitors having hydrotreating catalytic activity include Mo, W, Ni, Co, Fe, P, B, Pt, Pd, Rh, and Ru.
[0021]
In addition, a compound suitable as a pH adjuster for changing the pH of the hydrosol alternately and repeatedly between the precipitation region and the dissolution region is a raw material titanium tetrachloride, titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, Ferrous sulfate, ferric sulfate, ferrous chloride, ferric chloride, ferrous nitrate, ferric nitrate, nickel nitrate, nickel sulfate, nickel chloride, cobalt nitrate, cobalt sulfate, cobalt chloride, manganese nitrate , Manganese sulfate, manganese chloride, yttrium nitrate, yttrium sulfate, yttrium chloride and nitric acid (HNOThree), Hydrochloric acid (HCl), sulfuric acid (H2SOFour), Carbonic acid (H2COThree), Formic acid (HCOOH), acetic acid (CHThreeCOOH) and other acids and ammonia (NHThree), Sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na2COThree), Potassium carbonate (K2COThree), Sodium bicarbonate (NaHCO3)Three), Potassium bicarbonate (KHCO)Three), Potassium sodium bicarbonate (KNaCO)Three) And the like. These can be used alone or in a mixture of two or more.
[0022]
[Method for Producing Porous Group 4 Metal Oxide]
(Production of Group 4 metal hydrated oxide)
A hydrosol, hydrogel or dried product of a Group 4 metal hydrated oxide,2・ NH2The conditions for producing the Group 4 metal-containing oxide represented by O having an n value of 0.02 or more are the porous Group 4 metal oxide (MO2) The concentration is 1 to 20% by weight, preferably 3 to 15% by weight, the reaction temperature is from room temperature to 300 ° C., preferably from room temperature to 180 ° C., more preferably from room temperature to 100 ° C., and the reaction pressure is from normal pressure to 3.0 MPa. The pressure is preferably from normal pressure to 0.9 MPa, more preferably from normal pressure to 0.1 MPa, and the pH is in the range from 0.5 to 11, preferably from 1.0 to 10 by neutralization or hydrolysis with an alkali. A Group metal hydrated oxide is produced.
[0023]
(Addition of particle growth inhibitor)
General formula MO2・ NH2In the hydrosol or hydrogel of a Group 4 metal-containing oxide represented by O (wherein M represents a Group 4 metal and n is 0.02 or more), one kind as a particle growth inhibitor or Two or more kinds of anions, or cations, or these anions and cations are added. In this case, when the particle growth inhibitor is an anion, it is preferably added at a pH lower than the isoelectric point of the group 4 metal oxide. In addition, when the particle growth inhibitor is a cation, it is preferably added at a pH equal to or higher than the isoelectric point of the group 4 metal oxide. Furthermore, when the particle growth inhibitor is an anion or cation. Are preferably added simultaneously at a pH lower than the isoelectric point of the Group 4 metal oxide. This is because substitution by ion exchange or the like proceeds more effectively. And about the addition amount of these particle growth inhibitors, 0.06-6g equivalent with respect to 100g of group 4 metal oxides, Preferably 0.1-5g equivalent is added, and the aging time is 0.1 to 100 degreeC. Hold for -5 hours, preferably 0.2-3 hours.
In addition, it is effective to add a particle growth inhibitor to the hydrosol in the production stage and the hydrogel in the production stage.
[0024]
For example, in the case of titanium oxide, the hydrous titanium oxide is washed, and one or more kinds of anions are added at a pH of less than 6.1, which is the isoelectric point of anatase of titanium oxide as a particle growth inhibitor, or the isoelectric point is exceeded. In the case of adding one or more kinds of cations at the same pH, and simultaneously adding anions and cations, 0.06 to 6 g equivalents, preferably 0.1 to 5 g equivalents per 100 g of titanium oxide, at a pH lower than the isoelectric point, The aging time is 0.1 to 5 hours, preferably 0.2 to 3 hours at room temperature to 100 ° C.
[0025]
As a method for adding the particle growth inhibitor, a direct kneading method can also be used. In this method, a particle growth inhibitor is added directly to a gel or a dried product in an amount of 0.05 to 5 g equivalent, preferably 0.1 to 4 g equivalent, per 100 g of Group 4 metal oxide. In the temperature range of 0.1 to 5 hours, preferably 0.2 to 3 hours.
[0026]
(Drying and firing conditions)
The water content on the basis of the Group 4 metal oxide is 30 to 900% by weight, preferably 50 to 700% by weight, filtered and dehydrated, molded into a required shape, and a drying temperature of 40 to 350 ° C., preferably 80 to 200 ° C. The drying time is 0.5 to 24 hours, preferably 80 to 200 ° C., and the temperature is 350 to 1200 ° C., preferably 400 to 700 ° C.
[0027]
In addition, as for the method for producing a hydrosol of a Group 4 metal-containing oxide having a seed generation step and a hydrosol synthesis step, the method described in JP-B-60-50,721 can be specifically exemplified. .
That is, for the seed production step, conventional methods such as a heterogeneous precipitation method, a uniform precipitation method, a coprecipitation method, an ion exchange method, a hydrolysis method, and a metal dissolution method can be employed. For the hydrosol synthesis step, an aqueous solution of a Group 4 metal compound and / or a pH adjuster are alternately added to the hydrosol of the Group 4 metal-containing oxide obtained in the seed generation step, The hydrosol precipitation pH region refers to a pH region that can solubilize a fine particle hydrosol, and the hydrosol deposition pH region is a growth of hydrosol particles. And the pH range where aggregation occurs. Further, in this hydrosol synthesis step, treatments such as aging, washing, and solid content adjustment are performed as necessary to obtain a hydrosol or hydrogel of a Group 4 metal hydrated oxide having desired properties.
[0028]
In the production of the Group 4 metal oxide, the production conditions of the Group 4 metal hydrated oxide are as follows: the pH of the precipitation region in each stage swinging the pH is 0.5 to 11, the concentration is 0.1 to 20% by weight, The temperature is from room temperature to 300 ° C., and the holding time is 0.01 to 0.5 hours, preferably 0.02 to 0.3 hours. Further, the pH of the dissolution region of the Group 4 metal-containing oxide is preferably from 0 to 3, the concentration is from 0.1 to 20% by weight, the temperature is from room temperature to 300 ° C., and the holding time is from 0.02 to 5 hours. . In addition, the number of times of holding alternately in the precipitation region and the dissolution region is preferably in the range of 2 to 20 times.
[0029]
For example, in the case of titanium oxide, the production conditions at each stage of swinging the pH of the hydrous titanium oxide are as follows: the pH of the precipitation region is 1.0 to 10; the concentration is 0.1 to 15% by weight; ℃, holding time is 0.01 to 0.5 hours, preferably 0.02 to 0.3 hours, pH of dissolution region is 0 to 2, concentration is 0.1 to 15% by weight, temperature is from normal temperature to 180 ° C The holding time is preferably in the range of 0.02 to 5 hours. In addition, the number of times of alternately holding in the precipitation region and the dissolution region is preferably in the range of 2 to 10 times.
[0030]
The porous group 4 metal oxide obtained by the method of the present invention is useful for applications such as a catalyst carrier, a catalyst, a desiccant, an adsorbent, and a filler, but in particular, the porous 4 obtained by the method of the present invention. Group metal oxide is 80m2Hydroprocessing (desulfurization, denitrification, demetallization, asphaltene decomposition, aromatic hydrogenation) due to the characteristics such as high specific surface area of more than / g and pore sharpness degree (definition will be described later) 30% or more , Hydrocracking, alkylation, Fischer-Tropsch, flue gas denitration, photoreaction and the like can be used as a high-performance catalyst carrier or catalyst. 80m2When the specific surface area is less than / g, the desired reaction activity is hardly exhibited. Moreover, the selectivity of reaction will fall that a pore sharpness degree is 30% or less.
[0031]
[Measurement of physical properties]
(Pore sharpness)
Regarding the cumulative pore distribution curve measured by the mercury porosimeter, first, the vertical axis indicating the cumulative pore volume and the horizontal axis indicating the pore diameter (Å), at (1/2) PV of the total pore volume (PVT) The pore diameter (median diameter) is determined. Next, the pore volume (PVM) within a pore diameter range of ± 5% in the logarithmic value of the median diameter is obtained, and the fine volume is calculated from the pore volume (PVM) and the total pore volume (PVT) by the following formula. The degree of pore sharpness representing the degree of sharpness of the pore distribution is obtained.
Pore sharpness = {pore volume (PVM) / total pore volume (PVT)} * 100
The pore sharpness degree defined here is a factor for evaluating the optimum degree of pores for the reaction with respect to the total pore volume. The larger the pore sharpness degree, the sharper the pore distribution. This is preferable.
[0032]
(Measurement method of specific surface area)
The specific surface areas of the catalyst and the carrier were measured by the BET three-point method, and Macsorb Model-1201 manufactured by Mountec Co., Ltd. was used.
[0033]
(Measurement method of pore distribution)
The pore volume and pore distribution of the catalyst and the carrier were measured by a mercury intrusion method at a measurement pressure of 414 MPa, and Autopore 9200 model manufactured by Shimadzu Corporation was used as the measurement instrument.
[0034]
(Measurement method of crystal structure)
The crystal structure of the catalyst and the support was measured by X-ray diffraction, and PW3710 manufactured by PHILIPS was used as a measuring instrument.
[0035]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the present invention will be described in detail based on examples and comparative examples.
[0036]
Example 1
[Preparation of hydrosol]
(Preparation of titanium tetrachloride aqueous solution)
Titanium tetrachloride (TiCl) cooled in pure water with iceFour) 1 kg was gradually added to prepare an aqueous titanium tetrachloride solution having a titanium oxide equivalent concentration of 210 g / liter.
(14wt% NHFourPreparation of OH aqueous solution)
28wt% NHFourDilute OH twice and add 14wt% NHFourAn aqueous OH solution was prepared.
[0037]
(Hydrosol synthesis process)
Next, 10 liters of pure water was placed in a 30 liter vessel equipped with a stirrer, and 1.5 liters of the titanium tetrachloride aqueous solution was added while stirring to lower the pH to 0.5 or lower.
In this solution, the above 14 wt% NHFour2.3 OH aqueous solution was added to raise the pH to 7 and left for about 5 minutes.
[0038]
(Filtering and washing)
After completion of the hydrosol synthesis step, the mixture was filtered, and the resulting cake was washed with pure water, and chlorine (Cl-) Was repeated until no titer was confirmed, and a titania hydrosol was obtained.
[0039]
(Preparation of dried product)
The titania hydrosol obtained as described above was filtered by suction, dehydrated until the water content was about 50% by weight, and then molded using a die having a hole diameter of 1.5 mmφ. And dried for 3 hours to obtain a titania dry molded product.
[0040]
(Particle growth inhibitor addition process)
The titania dry molding obtained above was immersed in an aqueous solution containing 16.3% by weight of ammonium paramolybdate on an oxide basis per titanium oxide, allowed to stand at room temperature for 2 hours, and then filtered through 5C filter paper. As a result, a molybdenum support was obtained.
[0041]
(Dry firing process)
The obtained molybdenum-supported product was dried at 120 ° C. for 3 hours and then calcined at 500 ° C. for 3 hours to obtain a molybdenum-supported titania catalyst.
Table 1 shows the physical properties of the obtained molybdenum-supporting titania catalyst.
[0042]
Example 2
A hydrosol was synthesized in the same manner as in Example 1, 1.5 liters of the above aqueous titanium tetrachloride solution was added with stirring, the pH was lowered to 0.5 again, and then allowed to stand for 5 minutes, then 14 wt% NHFour2.8 liters of OH aqueous solution was added to raise the pH to 7 again and left for another 5 minutes.
These operations were repeated three more times, and the hydrosol dissolution pH range (pH 0.5) and the hydrosol deposition pH range (pH 7) were alternately changed 5 times in total.
The subsequent washing, filtration, molding, drying, particle growth inhibitor addition step, and drying and firing step were the same as in Example 1.
Table 1 shows the physical properties of the obtained molybdenum-supporting titania catalyst.
[0043]
Example 3
A phosphorus-supported titania catalyst was obtained in the same manner as in Example 2 except that 8% by weight of phosphoric acid on an oxide basis per titanium oxide was used as the particle growth inhibitor.
The physical properties of the obtained catalyst are shown in Table 1.
[0044]
[Table 1]
Example 4
The washed hydrosol of Example 2 was immersed in an aqueous solution containing 16.3% by weight of ammonium paramolybdate on an oxide basis per titanium oxide, allowed to stand at room temperature for 2 hours, suction filtered, and water content. It dehydrated until it became 50 weight%. Subsequently, it shape | molded using the die | dye with a hole diameter of 1.5 mm (phi), and after drying the obtained molded object at 120 degreeC for 3 hours, it baked at 500 degreeC for 3 hours, and obtained the molybdenum carrying | support titania catalyst.
Table 2 shows the physical properties of the obtained catalyst.
[0046]
Example 5
The filtered hydrogel of Example 2 was immersed in an aqueous solution containing 8% by weight of phosphoric acid on an oxide basis per titanium oxide, allowed to stand at room temperature for 2 hours, and then suction filtered to obtain a water content of 50% by weight. Until dehydrated. Subsequently, it shape | molded using the die | dye of hole diameter 1.5mm (phi), and after drying the obtained molded object at 120 degreeC for 3 hours, it baked at 500 degreeC for 3 hours, and obtained the phosphorus carrying | support titania catalyst.
Table 2 shows the physical properties of the obtained catalyst.
[0047]
Example 6
A tungsten-supported titania catalyst was obtained in the same manner as in Example 4 except that 20.6 wt% ammonium metatungstate based on oxide per titanium oxide was used as the particle growth inhibitor.
Table 2 shows the physical properties of the obtained catalyst.
[0048]
[Table 2]
Example 7
In a hydrogel after filtration using titanium sulfate as a raw material in the same manner as in Example 5, sulfuric acid was added as a particle growth inhibitor, and SO was added per titanium oxide.ThreeA sulfuric acid-supported titania catalyst was obtained in the same manner as in Example 5 except that 9% by weight was added on the basis.
Table 3 shows the physical properties of the obtained catalyst.
[0050]
Example 8
A boria-supported titania catalyst was obtained in the same manner as in Example 4 except that 3.9% by weight of boric acid based on oxide per titanium oxide was used as the particle growth inhibitor.
Table 3 shows the physical properties of the obtained catalyst.
[0051]
Example 9
An iron-supported titania catalyst was obtained in the same manner as in Example 5 except that 9.0% by weight of ferrous sulfate was used as the particle growth inhibitor based on the metal oxide per titanium oxide.
Table 3 shows the physical properties of the obtained catalyst.
[0052]
[Table 3]
Example 10
A nickel-supported titania catalyst was obtained in the same manner as in Example 5 except that 8.4% by weight of nickel nitrate based on oxide per titanium oxide was used as the particle growth inhibitor.
Table 4 shows the physical properties of the obtained catalyst.
[0054]
Example 11
Phosphorus / molybdenum-containing titania as in Example 5 except that 3.0% by weight phosphoric acid and 10.0% by weight ammonium paramolybdate on a titanium oxide basis were simultaneously used as the particle growth inhibitor. A catalyst was obtained.
Table 4 shows the physical properties of the obtained catalyst.
[0055]
Example 12
Cobalt / molybdenum supported in the same manner as in Example 4 except that 3.0% by weight of cobalt nitrate and 10.0% by weight of ammonium paramolybdate were simultaneously used as particle growth inhibitors based on oxides per titanium oxide. A titania catalyst was obtained.
Table 4 shows the physical properties of the obtained catalyst.
[0056]
[Table 4]
Example 13
Nickel / molybdenum supported in the same manner as in Example 4 except that 3.0% by weight of nickel nitrate and 10.0% by weight of ammonium paramolybdate were simultaneously used as the particle growth inhibitor on an oxide basis per titanium oxide. A titania catalyst was obtained.
Table 5 shows the physical properties of the obtained catalyst.
[0058]
Example 14
Example 5 except that 2.0% by weight phosphoric acid, 8.0% by weight ammonium paramolybdate and 2.0% by weight cobalt nitrate were simultaneously used as grain growth inhibitors on an oxide basis per titanium oxide. In the same manner as above, a phosphorus / molybdenum / cobalt-supported titania catalyst was obtained.
Table 5 shows the physical properties of the obtained catalyst.
[0059]
Example 15
Examples were used, except that 2.0% by weight phosphoric acid, 8.0% by weight ammonium paramolybdate and 2.0% by weight nickel nitrate were simultaneously used as grain growth inhibitors on an oxide basis per titanium oxide. In the same manner as in Example 5, a phosphorus / molybdenum / nickel-supported titania catalyst was obtained.
Table 5 shows the physical properties of the obtained catalyst.
[0060]
[Table 5]
Example 16
Implemented except that 2.0 wt.% Nickel nitrate, 8.0 wt.% Ammonium paramolybdate and 2.0 wt.% Cobalt nitrate were simultaneously used as particle growth inhibitors on an oxide basis per titanium oxide. In the same manner as in Example 5, a nickel / molybdenum / cobalt-supported titania catalyst was obtained.
Table 6 shows the physical properties of the obtained catalyst.
[0062]
Example 17
SO per titanium oxide as a particle growth inhibitorThreeSame as Example 7 except that 5 wt% sulfuric acid on a basis, 8.0 wt% ammonium paramolybdate on a metal oxide basis and 2.0 wt% nickel nitrate on a metal oxide basis were used. As a result, a titania catalyst supported on sulfuric acid / molybdenum / nickel was obtained.
Table 6 shows the physical properties of the obtained catalyst.
[0063]
Example 18
Examples were used, except that 2.0% by weight phosphoric acid, 8.0% by weight ammonium metatungstate and 2.0% by weight nickel nitrate were simultaneously used as grain growth inhibitors on an oxide basis per titanium oxide. In the same manner as in Example 4, a phosphorus / tungsten / nickel-supported titania catalyst was obtained.
Table 6 shows the physical properties of the obtained catalyst.
[0064]
[Table 6]
Example 19
A phosphorus-supported titania catalyst was obtained in the same manner as in Example 3 except that the method for adding the particle growth inhibitor was changed from immersion to impregnation by the pore filling method.
Table 7 shows the physical properties of the obtained catalyst.
[0066]
Example 20
A phosphorus-supported titania catalyst was obtained in the same manner as in Example 5 except that the method for adding the particle growth inhibitor was changed from immersion to direct kneading.
Table 7 shows the physical properties of the obtained catalyst.
[0067]
Example 21
A phosphorus-supported titania catalyst was obtained in the same manner as in Example 4 except that 8% by weight of phosphoric acid based on oxide per titanium oxide was used as the particle growth inhibitor.
Table 7 shows the physical properties of the obtained catalyst.
[0068]
[Table 7]
Example 22
A molybdenum-supported titania catalyst was obtained in the same manner as in Example 4 except that 30.3% by weight of ammonium paramolybdate on an oxide basis per titanium oxide was used as a particle growth inhibitor.
Table 8 shows the physical properties of the obtained catalyst.
[0070]
Example 23
A phosphorus-supported titania catalyst was obtained in the same manner as in Example 5 except that the calcination temperature was changed to 350 ° C.
Table 8 shows the physical properties of the obtained catalyst.
[0071]
Example 24
A molybdenum-supported titania catalyst was prepared in the same manner as in Example 5 except that 16.3% by weight of ammonium paramolybdate on an oxide basis per titanium oxide was used as the particle growth inhibitor and the calcination temperature was changed to 600 ° C. Obtained.
Table 8 shows the physical properties of the obtained catalyst.
[0072]
[Table 8]
Example 25
A phosphorus-supported titania catalyst was obtained in the same manner as in Example 5 except that the calcination temperature was changed to 200 ° C.
Table 9 shows the physical properties of the obtained catalyst.
[0074]
Example 26
A molybdenum-supported titania catalyst was obtained in the same manner as in Example 24 except that the sol synthesis temperature condition in Example 24 was changed to 95 ° C.
Table 9 shows the physical properties of the obtained catalyst.
[0075]
Example 27
A molybdenum-supported titania catalyst was obtained in the same manner as in Example 24 except that the sol synthesis temperature condition in Example 24 was changed to 200 ° C.
Table 9 shows the physical properties of the obtained catalyst.
[0076]
Example 28
A zirconia hydrogel after filtration in which the raw material was zirconium oxychloride in the same manner as in Example 2 was immersed in an aqueous solution containing 16.3% by weight ammonium paramolybdate on the oxide basis per zirconium oxide, and at room temperature. After standing for 2 hours, the solution was filtered by suction and dehydrated until the water content reached 50% by weight. Subsequently, it shape | molded using the die | dye with a hole diameter of 1.5 mm (phi), and after drying the obtained molded object at 120 degreeC for 3 hours, it baked at 500 degreeC for 3 hours, and obtained the molybdenum carrying | support zirconia catalyst.
Table 9 shows the physical properties of the obtained catalyst.
[0077]
[Table 9]
Comparative Example 1
Titanium tetrachloride aqueous solution and 14wt% NHFourAn aqueous OH solution was continuously mixed under a synthesis temperature condition of 95 ° C. to obtain a titania hydrosol. The obtained titania hydrosol was filtered, washed with water three times, then molded, and then calcined at 500 ° C. for 3 hours to produce a titania carrier.
Table 10 shows the physical properties of the obtained titania carrier.
[0079]
Comparative Example 2
The titania-molded dried product before addition of the particle growth inhibitor obtained in Example 2 was fired at 500 ° C. to produce a titania carrier.
Table 10 shows the physical properties of the obtained titania carrier.
[0080]
Comparative Example 3
The titania molded product before the addition of the particle growth inhibitor obtained in Example 2 was dried at 370 ° C., and the water content (n) of the hydrated oxide was adjusted to 0.01. A molybdenum-supported titania catalyst was obtained in the same manner as in Example 2 except that 16.3% by weight of ammonium paramolybdate based on the oxide was added.
Table 10 shows the physical properties of the obtained catalyst.
[0081]
[Table 10]
Example 29
Using a small flow reactor, vacuum gas oil (nitrogen concentration 0.2% by weight) as a raw material, reaction temperature 370 ° C., reaction pressure (hydrogen partial pressure) 8.0 MPa, LHSV2-1, H2/ Oil ratio 500NmThree/ Kl reaction conditions, the catalyst of phosphorus / molybdenum / nickel supported titania of Example 15 (BET specific surface area of 167 m)2/ G) was used for hydrogenation treatment. The nitrogen concentration of the resulting oil was 0.022% by weight.
[0083]
Comparative Example 4
Catalyzed commercially available titania as catalyst, BET specific surface area 42m2/ G Ni / Mo-supported titania catalyst (Ni: 2.4 wt% / Mo: 16.7 wt%) was used, and hydrogenation treatment was performed in the same manner as in Example 29 above. As a result of this hydrogenation treatment, the nitrogen concentration of the product oil was 0.10% by weight.
When the denitrification reaction rate was determined using the denitrification reaction as a primary reaction, the catalyst of Example 15 showed about 3.5 times the denitrification activity as compared with the catalyst of Comparative Example 4.
[0084]
Example 30
Using a small-sized flow-type reaction apparatus, starting from normal pressure light oil (sulfur concentration: 1.3% by weight), reaction temperature of 350 ° C., reaction pressure (hydrogen partial pressure) of 5.0 MPa, LHSV2-1, H2/ Oil ratio 200NmThree/ Kl reaction conditions, the catalyst of phosphorus / molybdenum / cobalt-supported titania of Example 14 (BET specific surface area of 149 m)2/ G) was used for hydrogenation treatment. The resulting product oil had a sulfur concentration of 80 ppm.
[0085]
Comparative Example 5
Catalyzed commercially available titania as catalyst, BET specific surface area 40m2Hydrogenation treatment was performed in the same manner as in Example 30 except that a Co / Mo-supported titania catalyst (Co: 3.9 wt% / Mo: 13.3 wt%) was used. As a result of this hydrogenation treatment, the sulfur concentration of the product oil was 450 ppm.
When the desulfurization reaction rate was determined using the desulfurization reaction as the 1.5th order reaction, the catalyst of Example 14 exhibited a desulfurization activity approximately 3.8 times that of the catalyst of Comparative Example 5.
[0086]
【The invention's effect】
According to the present invention, a porous group 4 metal oxide having not only a large specific surface area but also excellent thermal stability can be easily produced. In addition, by using a hydrosol of a Group 4 metal hydrous oxide having a controlled sharp pore size distribution, not only has excellent reaction selectivity, but also has a large specific surface area and excellent catalytic activity. At the same time, it is excellent in thermal stability, and a porous Group 4 metal oxide useful as a Group 4 metal catalyst or catalyst support can be easily produced.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between heat treatment temperature and specific surface area in Comparative Example 2. FIG.
FIG. 2 is a graph showing the relationship between the firing time and the specific surface area of Example 23.
FIG. 3 is an X-ray diffraction pattern of fired products of comparative examples and examples.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000213535A JP3755732B2 (en) | 2000-07-13 | 2000-07-13 | Method for producing porous group 4 metal oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000213535A JP3755732B2 (en) | 2000-07-13 | 2000-07-13 | Method for producing porous group 4 metal oxide |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005177207A Division JP4515337B2 (en) | 2005-06-17 | 2005-06-17 | Porous titania for hydrotreating and hydrotreating method |
| JP2005177206A Division JP4220495B2 (en) | 2005-06-17 | 2005-06-17 | Titanium oxide dried product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002028485A JP2002028485A (en) | 2002-01-29 |
| JP3755732B2 true JP3755732B2 (en) | 2006-03-15 |
Family
ID=18709273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000213535A Expired - Fee Related JP3755732B2 (en) | 2000-07-13 | 2000-07-13 | Method for producing porous group 4 metal oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3755732B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2264197B1 (en) * | 2002-07-08 | 2013-01-16 | Basf Corporation | Metal compound removal |
| CN100417589C (en) * | 2003-12-25 | 2008-09-10 | 千代田化工建设株式会社 | Layered porous titanium oxide, process for producing the same, and catalyst comprising the same |
| US7491676B2 (en) * | 2004-10-19 | 2009-02-17 | Millennium Inorganic Chemicals | High activity titania supported metal oxide DeNOx catalysts |
| JP5002136B2 (en) * | 2005-06-17 | 2012-08-15 | 千代田化工建設株式会社 | Catalyst composition for hydrotreating light hydrocarbon oil, process for producing the same, and hydrorefining process for light hydrocarbon oil |
| WO2007021037A1 (en) * | 2005-08-19 | 2007-02-22 | Kyoto University | Inorganic porous object and process for producing the same |
| JP4934417B2 (en) * | 2006-12-08 | 2012-05-16 | 千代田化工建設株式会社 | Method for producing metal-supported catalyst |
| JP4928245B2 (en) * | 2006-12-11 | 2012-05-09 | 千代田化工建設株式会社 | Method for producing metal-supported catalyst |
| JP5113034B2 (en) | 2008-12-26 | 2013-01-09 | Ｕｄトラックス株式会社 | Power storage device and module power storage unit |
| JP5275091B2 (en) * | 2009-03-06 | 2013-08-28 | 東邦チタニウム株式会社 | Method for producing titanium oxide powder |
| JP5599212B2 (en) | 2010-03-30 | 2014-10-01 | 千代田化工建設株式会社 | Hydrocarbon oil hydrotreating catalyst, method for producing the same, and hydrotreating method for hydrocarbon oil using the same |
| SG11201500226QA (en) | 2012-07-19 | 2015-03-30 | Chiyoda Corp | Method for reactivating used hydrogenation treatment titania catalyst, and regenerated hydrogenation treatment titania catalyst |
-
2000
- 2000-07-13 JP JP2000213535A patent/JP3755732B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002028485A (en) | 2002-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7943115B2 (en) | Porous 4 group metal oxide and method for preparation thereof | |
| EP2550235B1 (en) | Method for making highly porous, stable aluminium oxide with a controlled pore structure | |
| KR101127384B1 (en) | Nano-Structured Particles with High Thermal Stability | |
| CA2841803C (en) | Method for producing composites of aluminum oxide and cerium/zirconium mixed oxides | |
| US5021392A (en) | High porosity titania-zirconia catalyst support prepared by a process | |
| JP5564109B2 (en) | Composition comprising cerium oxide and zirconium oxide with specific porosity, its preparation method and its use in catalysis | |
| US10479760B2 (en) | Synthetic methods for the preparation of propylene ammoxidation catalysts | |
| JP3755732B2 (en) | Method for producing porous group 4 metal oxide | |
| JP5722804B2 (en) | Activated zirconium oxide catalyst support | |
| US10479759B2 (en) | Synthetic methods for the preparation of propylene ammoxidation catalysts | |
| JP5574238B2 (en) | Improved production process of high surface area nanoparticulate vanadium phosphate catalysts and their product derivatives | |
| JP4515337B2 (en) | Porous titania for hydrotreating and hydrotreating method | |
| US9079164B2 (en) | Single reaction synthesis of texturized catalysts | |
| KR102706685B1 (en) | Porous aluminum hydrate | |
| JPWO2005063618A1 (en) | Laminated porous titanium oxide, method for producing the same, and catalyst using the same | |
| WO2018069759A1 (en) | Copper/zinc/aluminium catalyst for the methanol synthesis prepared from a binary zinc-aluminium precursor solution | |
| JP4220495B2 (en) | Titanium oxide dried product | |
| Montoya et al. | The effect of temperature on the structural and textural evolution of sol–gel Al2O3–TiO2 mixed oxides | |
| Zhou et al. | Facile synthesis of high surface area nanostructured ceria-zirconia-yttria-lanthana solid solutions with the assistance of lauric acid and dodecylamine | |
| JP2004033819A (en) | Porous titanium oxide carrier, catalyst using the same and manufacturing method for porous titanium oxide carrier | |
| US5021385A (en) | Catalyst comprising a titania-zirconia support and supported catalyst prepared by a process | |
| CN1781605B (en) | Method for manufacturing catalyst for hydrogenation of hydrocarbon oil and method for hydrogenation refining | |
| JP4054562B2 (en) | Hydrocarbon oil hydrotreating catalyst and method for producing the same | |
| JP2007112655A (en) | New titanium oxide and method for synthesizing the new titanium oxide | |
| JP4054563B2 (en) | Catalyst for hydrotreating hydrocarbon oil, method for producing the same, and hydrorefining method using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20050131 |
|
| A975 | Report on accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A971005 Effective date: 20050223 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050419 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050617 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20051213 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20051215 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 3755732 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090106 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100106 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110106 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120106 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120106 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130106 Year of fee payment: 7 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140106 Year of fee payment: 8 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |